Dichloro diether esters



Patented Nov. 13, 1951 UNITED STATES PATENT" OFFICE 2,575,009

of Delaware No Drawing. Application August 19, 1949, Serial No. 111,333

1 This invention deals with dichloro diether esters of the formula and with a method for their preparation. In this formula R represents an alkyl group of not over four carbon atoms and R represents an aliphatic or an aryl group. This invention also concerns a method for the preparation of these compounds. These compounds are prepared by reacting an alcohol or a phenol, R'OH, with an alkyl trichloroalkoxypropionate, a compound of the formula ROCHCICClzCOOR preferably between 20 C. and 110 C. Higher temperatures may, however, .be used. The reaction may be effected by mixing the two materials and taking ofl hydrogen chloride. Heating may be desirable to initiate and/or to complete the reaction. The reaction may be efiected in the presence of an inert organic solvent, if desired.

It is sometimes helpful to have present an inorganic material which absorbs hydrogen chloride. such as calcium carbonate, or sodium bicarbonate. When the reaction is run under reduced pressure, hydrogen chloride may be taken off as a gas or when a volatile organic solvent is used, it may be swept out with vapors of the solvent.

The above.starting materials, alkyl trichloroalkoxypropionates, are obtained by a series of reactions which may be'traced back to acetylene andalkyl carbonates. Thus, the alkyl trichloroalkoxypropionates are obtained by chlorinating alkyl fl-alkoxy-achloroacrylates, which are in turn obtained from alkyl fi-alkoxyacrylates. These last are available through the reaction of acetylene and alkyl carbonates in the presence of anhydrous strongly basic alkaline catalysts. x

This last reaction is fully described in application Serial No. 52,607, filed by Croxall and Schneider on October 2, 1948, now Patent No. 2,535,012. Dialkyl carbonates (RO)2CO, such as methyl, ethyl, propyl, or butyl carbonates, or the like, are reacted at 20 to 110 C. with acetylene in the presence of alkaline catalysts, such as alkali metal acetylides, alkali metal alcoholates, or quaternary ammonium alkoxides. Typical examples of catalysts are sodium acetylide, potassium acetylide, sodium methylate, potassium ethylate, sodium butoxide, benzyl trimethyl, ammonium methoxidaethoxideor tertsbutoxid'e. I

8 Claims. (01. 260-413) By this reaction, there are formed alkyl p-alkoxyacrylates, alkyl 5,5-dialkoxyproprionates, dialkyl dialkoxysuccinates, and dialkyl alkoxymaleates. These various compounds can be separated by distillation when so desired, or more conveniently the first two esters are collected in one fraction and the latter two in another. ,A fraction which contains both alkyl fi-alkoxyacrylate and alkyl dialkoxypropionate may be taken and the dialkoxypropionate converted to alkoxyacrylate. It is, of course, feasible to fractionate alkoxyacrylate and dialkoxypropionate and to convert the latter to alkoxyacrylate.

This reaction in either case is accomplished by heating apmixture containing dialkoxypropionate or an alkyldialkoxypropionate itself in the pres ence of a dealcoholating catalyst and taking ofi a mole of alcohol per mole of dialkoxypropionate. This process is describedv in application ,Serial No. 52,608, filed by Croxall andS'chneider on 0ctober 2, 1948, now Patent No. 2,571,212.

Reaction of the alkyl ,S-alkoxyacrylates with chlorine is readily carried out at 5 C. to 20 C. to form an addition product, alkyl a,fi-di0h10l0- B-alkoxypropionate, which is dehydrohalogenated by heating at to 250 (3., whereby an alkyl a-chloro-B-alkoxyacrylate is formed. The full details of this reaction are presented in our application Serial No. 111,331, filed on even date, now U. S. Patent 2,526,007, issued October 17, 1950.

When these products are treated with one mole of chlorine per mole, they are converted into the starting materials 'for the present invention. This reaction is more fully described in our application Serial No. 111,332,.filed on even date, now U. S. Patent 2,526,008, issued October 1'7, 1950.

Examples will now be given to illustrate each of the above procedural steps leading to the alkyl a,a.-dichloro-,8, 8-dietherpropionates of this invention.

A. PREPARATION OF DIETHER PROPIO- NATES AND ETHEB ACRYLA'I'ES Erampl In an apparatus having a gas-tight, stainlesssteel stirrer, there was placed 225 grams of anhydrous ethyl alcohol. Small cubes of sodium were gradually added thereto in an amount of 30 grams. The sodium was dissolved with the formation of sodium ethylate; Excess alcohol was distilled ofi under reduced pressure. To the sodium ethylatethere was added 2200. grams of diethyl carbonate. The-reaction vessel was thenequipped with gas inlet and outlet tubes, manometer, and thermometer. It was fluished with nitrogen and heated to 80 C. Acetylene was passed in until the rate of absorption became very slow. The vessel and :contents were cooled and the flow of acetylene. discontinued Dilute aceticv acid was added to destroy the catalyst. Two layers formed. The upper oily layer was separated and frac;- tionally distilled. v

A forerun taken at atmospheric pressure consisted of ethyl alcohol and ethyl carbonate. Distillation was continued under reduced pressure. A fraction distilling at 65-=75 'C./2- 4 mm, con-- sisted of of ethyl fi-ethoxyacrylate and 90% of ethyl BJS-diethoxypropionate. 75 C lrnm. a fraction of pure ethyl fifi-diethoxypropionafte was obtained. Between 75 C./4 mm. and 114 C./3 mm., a mixture of ethyl p.B-diethoxypronio'- mate and diethy1 a,a-diethoxysuccinate was taken air. At 114-115 C./ 3-4 mun, thereiwasobtained a fraction consisting. of diethyl a,a-diethoxysuc'- cinate. On furtherdistillation. a fraction con-- taining this other succiria't'e and diethyl "aethoxymaleate 'was obtained.

In the same way other esters of carbonic acid and 'monohydric alcohols maybe reacted with acetylene to give ether acrylates and propi'onates as above. 'Other alkaline catalysts may 'be used in place of sodium 'e'th'yl'ate in amounts from 0.01% to 5% of. the weight of the carbonate. Typical esters thus available are methyl flmethoxyacrylate, meth'y 5. 3 dimethoxypropionate, propyl 'fi-propoxyacrylate, propyl Bfi-dipro'poxyprionate, isopropyl 'fi isopropoxyacrylate, butyl -'p-butoxyacrylate, butyl 'figfi-dibutoxypropionate. isobutyl ,8-isobutoii-yacrylate, etc.

B. CONVERSION OF 'pp-DlALKOXY PROP IO NATES to AIIKYL E-ALKOXYACRY- LATES w V Example 2 A mixture of I 192 grams "or ethyl mfl diethoxypro'pionate and one grampf sodiunr acid-sulfate wasplaced in'areaction vesselfequipped'with a short packed column and 'slowly' *heated; At about 80 0.. therejbeg'an to beevolved vapors ofeth'yl alcohol. Heating was continued with distillation of the"alc chol. Pot temperatures advanced to 150C. with overhead" temperatures of 78.5 C. to 80? C. A totalof 44.5 grams of ethyl alcohol was taken oil. Heating was continued andfat 85;5 --'8'6;5 -C./.1'9 mm.,- main fraction was taken which wasethylfl-ethoxyacrylate.

Example't In accordance "with "the method or Example 2, amixture of 96 grams of n-butyl fi,p-di(n-bu-' toxy)propionate and 0.25 gram of sodium acid sulfate was heated. 'At batch temperatureslof 110 160 0., there was evolved n butanol -with overhead temperatures of 110 to 114 C. The batch temperature 1 was "carried to 180 C. At 110-111 C./3 mm., there wasobtained the main fraction which consisted of butyl B-butoxyacrylate.

Ezrample4 'Theabove procedure was applied to a charge 'of'954-grams of methyl dfi-dimethoxypropionate and 0.1-gram of sodium acid sulfate. There were obtained 185 grams of methanol and'650 grams of methyl ft-methoxyacrylate.

The dealcoholating catalysts include both strongly acidic and basic materials, such as po tassium acid sulfateyp-toluene' sulfonic acid, sul- 4 furic acid, boric acid, zinc chloride, sulfonated cation exchange resins in their hydrogen form, alkali metal alcoholates, alkaline earth alcoholates, etc., amounts of 0.01% to 1% by weight generally suificient.

c. PREPARATION OF ALKYL d-CI-lLORO-fl- ALKOXYACRYLATES Example 5 There were mixed in a reaction vessel equipped with fstirrer, refiux'condenser, and gas inlet tube 216 parts by weight of ethyl B-ethoxyacrylate and 200 parts of chloroform. This mixture was cooled by use of a salted ice bath. Chlorine gas was'bubbled through the mixture while it was kept below 10 C. When an excess of chlorine had been added as shown by development of a yellow color, the passage of chlorine was discontinued. Excess chlorine andpart of the chloroform were removed under reduced pressure while the reaction mixture was gently warmed. The product was ethyl a,B-dichloro-B-ethoxypropionate in chloroform solution.

A mixture of 178.5 parts of ethyl fl-ethoxyacrylate and 250 parts of chloroform was reacted with chlorine as above. Excess chlorine and chloroform were taken off by heating. Hydrogen chloride was evolved and the materialin'the'reaction vessel was heated to 1501'60 C. for two hours. It was then fractionally distilled. A 'for'erun of a small amount of ethyl t -ethoxyacrylate was obtained at -150' C./61 mm. At C./61 mm., there was distilled ethyl chloro-c-ethoxyacrylate. It has a refractive index, of 1.4728. By analysis the product obtained contained 20.11% of chlorine. The theoretical chlorine content for ethyl a-chloro-fiethoxyacrylate is 19.85%. Theyield was-92 Example 6 Ethyl [1,[3 dichloro c ethoxypropionate was prepared as in Example 5 above. It was run very slowly into a mixture of 1.35 gram moles of triethylamine in 400 ml. of ethyl ether until 1.28 gram moles of the ether ester had beenadded. Triethylamine hydrochloride was formed and was separated by filtration. The ether was distilled off and the resulting material filtered-to remove additional triethylamine hydrochloride which had separated. It was then distilled-at 78-80 C./l mm. to give a 78% yield of 'ethyl a-chloro-,B-ethoxyacrylate.

Example 7 A solution of 116 parts by weight of methyl r methoxyacrylate in 250 parts of chloroform was cooled to 10 C. and treated with chlorine gas as in Example 5-. The temperature of the reaction mixture was kept between 2 and 10 C.'-by use of an ice-salt bath. As soon as a yellow color developed, excess chlorine was taken 01f along with most of the chloroform by stripping -under reduced pressure. The product thus obtained was methyl a,B-dichloro-;8-methoxypropionate.

A portion of this product was heated at C. for 1.5 hours. Hydrogen chloride was taken oif as it was evolved. The heated product was'then fractionally distilled. A forerun of methyl ,3- methoxyacrylate was taken off at 95-124 C./28 mm. At 124-128 C./28 mm., a fraction was distilled which corresponded in composition-to that of methyl a-chloro-/3-methoxyacrylate. The

- redistilled product boiled at 124'-125 C./28-mm.

and hada refractive index.=n pof 1.4838.

Example 8 (a) A mixture of 31.5 parts of butyl p-butoxy' acrylate in 75 parts of chloroform was cooled' to 5 C. and chlorine passed therethrough while the temperature was kept between and 8 C. by means of an ice-salt bath. The chloroform was distilled from the reaction mixture and the resulting material heated at 160-180 C. for an hour.- It was then distilled at low pressure. After a forerun of butyl p-butoxyacrylate, there was obtained a fraction of 18 parts which distilled at 135-146 C./4 mm. and corresponded in composition to butyl a-chloro-p-butoxyacrylate.

(b) A mixture of 89 parts of ethyl a-ChlOlO-fiethoxyacrylate, 112 parts of normal butyl alcohol, and 2 parts of p-toluene sulfonic acid was heated in a reaction vessel equipped with a packed distilling column topped with partial take-off head. Ethanol was distilled from the reaction mixture. When it was no longer obtained, the temperature was raised and butanol was taken off. The mixture was then subjected to fractional distillation at reduced pressure. A forerun of eight parts distilling at 90-122 C./4 mm. consisted of mixed ethyl a-chloro-,3-ethoxyacrylate and butyl a-chloro-B-butoxyacrylate. At 122-145 C./4 mm., there was obtained butyl a-chloro-fi-butoxyacrylate in an amount of 65 parts. This material was redistilled at 142-144 C./4 mm. to give a very pure product, which had a refractive index of 1.4674 and which contained by analysis 14.75% of chlorine (theory 14.76%). i

This last example also illustrates the fact that ether acrylates can be both transetherified and transesterified. By use of a mild dealcoholating catalyst, such as sodium acid sulfate, a smaller ether group may be replaced with a larger one without changing the ester group. Thus, ethylp-ethoxyacryl'ate is heated with butyl alcohol to give ethyl p-butoxyacrylate or with octyl alcohol to give ethyl p-octoxyacrylate. This interchange reaction is particularly useful to introduce other than an alkoxy group in the B-position,=such as benzoxy or cyclohexoxy. It provides a method for varying the term R, which need not, therefore, be identical in both the ether group and the'ester group. When such compounds are carried through the various steps herein described, there can be obtained compounds of the formula \CHO 01,0 0 o R in which the R groups are all different.

' g D. PREPARATION OF ALKYL a,a,fl-TRI- CHLORO-B-ALKOXYPROPIONATES Example 9 A solution of 50 parts by weight of methyl a-chloro-B-methoxyacrylate in 200 partsof chloroform was placed in a three-necked flask equipped with stirrer, reflux condenser, and gas inlet tube. The solution was stirred and cooled by means of an external ice-salt bath to about C.

Chlorine was bubbled into the solution while the temperature was maintained between 0 and 10 C. An excess of chlorine wasindicated when the reaction mixture began to develop a yellow color. The excess chlorine and the chloroform were stripped off and the reaction mixturewas fractionally distilled. At 64 to 67 C./2 mm., there was obtained a fraction which corresponded in composition to methyl g-trichloroepemethoxyr- 6 propionate in a yield of 83%. On redistillation this product had a refractive index, 11 of 1.4701.

Example 10 A solution of 100 parts by weight of ethyl a-chloro-p-ethoxyacry1ate in 250 parts by weight of chloroform was reacted with chlorine by the steps described in Example 9. At 90-97 C./ 1 mm., there was collected a fraction which contained the ethyl a s-trichloro-,8-ethoxypropionate. This was redistilled at 95-97 C./1 mm. The redistilled product had a refractive index, n of 1.4618. It contained by analysis 42.48% or chlorine. The theory for C7H1103C13 is 42.7%. The yield was 93%.

Example 11 In the same way butyl a-chloro-p-butoxyacrylate was chlorinated. The fraction collected at 130-139 C./1 mm., corresponded in composition to butyl a,a,5-trichloro-/3-butoxypropionate. The product as obtained contained 35.5% of chlorine.

The trichloro ether esters of the formula ROCHCICClzCOOR react with an alcohol or a phenol to give the compounds of this invention.

Suitable alcohols include any of the saturated monohydric aliphatic alchols, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tart-butyl, amyl, including tert.-amyl, hexyl, heptyl, octyl, Z-ethylhexyl, isononyl, 3,5,5,-trimethylhexyl, dodecyl, etc. Unsaturated alcohols, such as allyl, methallyl, crotyl, or undecenyl, may also be used. Cycle-containing alcohols, such as cyclohexyl, methylcyclohexyl, benzyl, butylbenzyl, phenoxyethyl, and so on are likewise effective. Furthermore, other monhydric alcohols, such as terpineol, nordihydrodicyclopentenyl, tetrahydrofurfuryl, cinnamyl, etc., may be used. 7

Phenols act in the same Way, phenol, cresol, xylenol, chlorophenol, 2,4-dichloropheno1, pentachlorophenol, bromophenol, methoxyphenol, acep3,,B-diether a,a-'dichloropropionates.

Example 12 .,(a-) A" solution of 18 parts by weight of ethyl ap-trichloro-;3-ethoxypropi0nate in 40 parts of anhydrous ethanol was treated with two drops of concentrated hydrochloric acid and heated on a steam bath under reflux for eight hours. Ethanol was then distilled off in an amount of 33 parts at overhead temperaturesof 77 to 80 C. A fraction of seven parts was taken at 20 C./17 mm. to C./ 2 mm. A fractionwas then distilled at 85-92 C./2 mm. It was identified as ethyl a,a-Cll0h10l'0- m5-die,thoxypropionate. It had a refractive index, n of 1.4488 and a density, d4 of 1.189. The distillate was found by analysis to contain 27.59% of chlorine. The theoretical chlorine content of, the compound, C9H16O4C12, is 27.60%. I

.(b) The'procedure of .Example 12 (a) above was; followed except thatno hydrochloric acid was added: to .Ithe' reaction: mixture. The fraction obantenna 7 tainedatBT-Q? J2 mm; was identified as ethyl wdichloro-pp-diethoxypropionate;' The fraction as obtained had a refractive index of 1.4450.

Example 13 Asolution of 22 parts by weight of methyl ptrichloro-B-methoxypropionate in 50 parts of dry methanol was heated under reflux for eight hours.

There was then distilled 45 parts of methan'oIa-t 66 C. Distillation was continued-under reduced pressure. At 62-66 C./4 mm., there was "ob tained a fraction of 12 parts which corresponded in composition to that of methyl a,a-d1Ch10fO-B48 dimethoxypropionate.

Example 14 A mixture of parts of butyl a,a,p-trichloro-fibutoxypropionate in parts of butanol was heated at reflux temperatures for 'four'hours. Butanol was then distilled from the reaction mixture and distillation was continued under reduced pressure. The fraction obtained at 134-139 C./2 mm. corresponded in composition to that of butyl a,a-dichloro-fl,fi-dibutoxypropionate.

Example 15 The procedure of the previous example was followed with a solution of 27 parts of 2-ethylhexyl e,a,,3-trichloro-fi-2-ethylhexoxypropionate in 50 parts of 2-ethylhexyl alcohol. The product was obtained as a fraction distilling at 1572-16! C./0.8-1.2 mm. It was 2-ethylhexyl a,adlOh1OI'O- ,8,,Bdl (2-ethylhexoxy) propionate.

Example 16 A mixture of 20 parts of ethyl a,a,fi-tli0h10l'0- fl-ethoxypropionate and 50 parts of tert-butanol was refluxed for 12 hours under a slightly reduced pressure from a water pump. The'temperature of the reaction mixture was about 80 C. Hydrogen chloride was taken off. Finally, the reaction mixture was heated to distill 011 the excess tert.-butanol and the reaction mixture was fractionated. The main fraction was obtained at 87 C./1 mm. It corresponded in composition to ethyl a,a-dichloro-,d-tert.-butoxy-fl-ethoxypropionate. It has a refractive index n ,of"114600.'

Example 1 7 A mixture of parts by weight of methyl Example 18 (a) A mixture of 80 parts ofethyl a,a.,B-f.richloro-c-ethoxypropionate and 32 parts of phenol was heated at 40 to C. for an hour. It was then held at about 60 C. while the pressure in the reaction vessel was reduced toabout70. mm. Hydrogen chloride was taken off. Themixture was then heated under reduced pressureand: fractionally distilled. A forerun of 18 parts of phenol was taken ofi. There wasthen obtained ethoxypropionate. At 137-145 C./4 mm., a fraction of 76 parts of ethyl a, di chloro-pethoxy s phenoxypropionate was obtained. The fraction contained by analysis 23.55% of chlorine (theory 23.1% This was redistilled at120i-l21 C.'/l mm. The redistilled material had a retrac t'ive index; 11 of 1.5037, and a density of 1239, and .a molecular refraction of 73.37 (theory 73.30). (b) A reaction vessel was charged. with parts by weight of ethyl 'a,ap-trich1oro-c-ethoxypro pionate' and 32 parts of phenol. This mixture was heated under atmospheric pressure at reflux temperaturesof 150-'-200 C. for 4.5 hours; Hydrogen chloridefiwas taken off by aid of a water pump. The reaction mixture was fractionall'y distilled. Unreacted'phenol was removed and at 'l0-13'7fv C./4 unreacted ethyl a,a,p-trichloro -p-eth oxypropionate was obtained. At l?'7'-145' (1/51. mm., there wasfldistilled a fraction containing ethyl u -dichloro-5-ethoxy-B-phenoxypropionate, amounting to 25 parts. At 148-150 C./4 mm., 46 parts of this product was obtained. The refractive index p of a center cut was 1.5050.

Example 19 A mixture of 62 parts of butyl a,a,, 3-tl'iCh10r0-flbutoxypropionate and 18 parts of phenol was heated on a steam bath,' first at atmospheric pressure and then under reduced pressure from a water pump. Hydrogen chloride was evolved and carried away. The reaction mixture was then fractionally distilled. After phenol had been taken off, a small fraction of butyl a,a,/3-t1i0hl0r0 B-butoxypropionate was obtained at 130 142 C./2 mm. At 163171 C./2 mm., there was obtained a fraction which corresponded in composition to butyl a,a-dichloro-p butoxy-fi-phenoxypropion'ate.

Example 20 ethoxy propionate and 27 parts of 2,4-dichloro-- phenol was heated up to 100 C. for an hour at atmospheric pressure. The mixture was then subjected to reduced-pressure from a water pump whilethe-temperature was held at to C.

The reaction mixture was then fractionally dis tilled. Unreacted starting materials were-taken oif between 70" and C./5 mm. At 171172 refraction of 84.33- (theory8304), and a densityof 1.360. By analysis vthe fraction contained 37.35% of chlorine. The theoretical value for the compound is 37.71

Example 21 .Amixture of 50 parts of ethyl a,a,p-trichloro-- p-ethoxypropionate and 22 parts of o-cresol was" heated on a steam bath for an hour at normal pressure and. for three hours under reduced pressure irom'a water pump. The reaction mixture was then fractionally distilled. The fraction taken at 136-146 C./2 mm. corresponded in composition to ethyl .1,-dichloro-p-ethoxy-;3-o-

' methylphenoxypropionate.

In the same way as shown above other monohydric phenols may be used with one or more ring substituents. The reaction is apparently a gen eral one for any compound having a phenolic "or alcoholiehydroxylgroup. I 1 a Y Example 23 There were mixed 50 parts by weight of ethyl a,a,fi-trichloro-p-ethoxypropionate and 53 parts of oleyl alcohol. The mixture was heated on a steam bath for three hours at normal pressure and then for three hours at 15-20 mm. pressure. Hydrogen chloride was evolved and taken off. The product was taken up in a little benzene, activated charcoal was added to the solution, and the solution was heated on the steam bath. The solution was then filtered and the filtrate heated under reduced pressure. After the solvent had been removed, the material was heated to 125 C./'1 mm. to strip off volatile material. There remained a straw-colored liquid which corresponds in composition to ethyl a,a-dich10l0- fl-ethoxy-p-octadecenoxypropionate.

Example 24 The steps of Example 23 were followed with a mixture of 25 parts of ethyl a,a, 8-tliCh10rO 8 ethoxypropionate and 37 parts of dodecyl alcohol. Stripping of the final product was accomplished at about 110 C. at 2 mm. The product was obtained as a colorless oil. It consisted chiefly of the desired product, ethyl a,a-diCh10lO-fiethoxy-/3-dodecoxypropionate.

Example 25 (a) A mixture of 50 parts of ethyl a,a,fi-trichloro-p-ethoxypropionate and 30 parts of tertbutylphenol was heated for an hour at 90-95 C. under normal pressure and then for three hours under reduced pressure from a water pump. During this time hydrogen chloride was taken off. The material was taken up in a little petroleum ether and washed with a 5% sodium hydroxide solution. The petroleum ether solution was separated and dried over a calcium sulfate drying agent. It was then heated and freed of solvent. Heating was carried to 125 C./1-2 mm. There remained a residue which corres onded to ethyl a,a-diCh1OIO-}3-th0Xy-flbutylphenoxypropionate.

(b) The above procedure was applied to a mixture of 22 parts of methyl ,a,,8-trichloro-flmethoxynropionate and 20 parts of p-a,a,'y,'ytetramethylbutylphenol. The residue corresponds to methyl (2,11, dichloro p methoxy ,3 octyl phenoxypropionate.

Example 26 A mixture of 25 parts of ethyl a,a,;3-tli0h10l0- p-ethoxypropionate and 14 parts of nitrophenol was heated on the steam bath for an hour at normal pressure and then for two hours under reduced pressure from a water pump. Hydrogen chloride was ta"en off during this time. The product was then taken up in toluene, charcoal was added, the mixture warmed, and the solution filtered. The filtrate was stripped of solvent to a temperature of C./1 mm. Ther remained a light yellow oil which corresponded in composition to ethyl a,a-dich1oro-,3-ethoxy-pnitrophenoxypropionate, having a nitrogen contentof 4.09%. 1

Example 27 The procedure of Example 25 was followed with a mixture of 50 parts of ethyl a,a, 3-tr1- chloro-;3-ethoxypropionate and 53 parts of pentachlorophenol. Stripping was carried to 110 C./l mm. The residue corresponded in composition closely to that for ethyl'a,a-dichloro-fl-ethoxy-p-pentachlorophenoxypropionate, containing 53.5% of chlorine.

Exactly the same reaction is obtained when methyl, propyl, or butyl esters of the trichloroalkoxypropionic acids are used in place of the ethyl compound, which has been shown for purposes of illustration and not limitation.

Finally, it may be noted that the reaction described and illustrated above is generally applicable to alcohols and phenols. The alcohol-need not be purely aliphatic, for arylaliphatic and cycloaliphatic groups are quite as useful and as effective as ethyl, allyl, butyl, octyl, and the like aliphatic hydrocarbon groups. Thus, methyl a,a,;8-trichloro- 8-methoxypropionate heated with a molecular equivalent of benzyl alcohol yields methyl a t-dichloro-p-benzoxy- 3-methoxypropionate, and ethyl a,a,p-trichloro-;3-ethoxy-propionate and cyclohexanol yield ethyl a,a-dichloro-scyclohexoxy-p-ethoxypropionate. Furthermore, it is found that a B-chlorine is replaced with a heterocyclic oxy group, as is readily shown by heating together an alkyl trichloroalkoxypropionate and tetrahydrofurfuryl alcohol. Hydrogen chloride is evolved and the tetrahydrofurfuroxy group introduced in place of a chlorine atom.

The diether esters of this invention are compatible with various types of resinous materials, serving as softeners and plasticizers therefor. Some of the compounds have insecticidal properties. For example, the methyl, ethyl, propyl and butyl esters of a,a-dich10r0-fi-a1kOXy-fl-(2,4-(11- chlorophenoxy) propionate are effective miticides. Ethyl a,a dichloro-,B-ethoxy p (methoxyphenoxy)propionate also has insecticidal properties. The compounds furthermore serve as chemical intermediates, having a plurality of reactive groups and positions.

We claim:

1. A process for preparing compounds of the formula CHCChC 00R which comprises reacting together a monohydroxy compound, R'OH, and an ester of the formula ROCHCICClzCOOR and splitting out HCl, R being an alkyl group of not over four carbon atoms and R being the non-hydroxylated residue of a member of the class consisting of monohydric aliphatic alcohols in which the residue is a hydrocarbon group, and monohydric phenols.

2. A process for preparing compounds of the formula 11 which comprises reacting itogether a monohydric a-liphaticwalcohol; ROHa and f an'e's'ter' of the for mula- ,-r,;" 1 I 1 1 5: 1 ROCHClCClzCOOR and splitting out: HQIQR bing'an' alkyl group of hot ovr' four c'arb'o'ri atoms' am n" being" an al1- phatic hydrocarbon group. 3. A process forpreparing compounds of the which comprises "reacting together a phenol, ROH; and ailestefi'offth formula RQCl-IQlCQlCQOR and splitting out HCl, R being an alkyl group of not overwfour carbon -'aton s sand -"R :heing 'th'e residue of-a monohydric' phenol. 1 4. A proces's fompreparingvethyl a,a-diCh10rO- p,;8diethoxypropionalteiwhich comprises reacting by heatin'g together ethanol 'andethyl r afi-trie chloro-fi-ethoxypropiona-te;- 1 11; 5; A=prooessfbr preparing methyl a,a-dichloro- -dimethoxypropionate which comprises re'act- 12 ing by heating together methanol and methyl a,a,;3-trichloro-fl-mthoitypiofiionate.

.6. A process for preparing hutyl a,a -q i chlorofifif-" i t 'i r i jh reqmp i es actin by heating 5 together butar iol and hutyl' days-trichloro-fi-butoiiypropionatef 1 "7. 'A' proc 'ss fofpreparing methyl a,a-clichloro 13-inethoxy-B-pheno$ ypropionate which comprises reacting by heating together phenol and methyl (m,3-trichloro-fi-methoxypropionate;

8. A process for preparing ethyl a',a-d i 0h1910- floxwyp 2piqn wh h c mprise reacting l n tse hq rah nol a eth l d,a,,3 -trichloro p ethoxypropionateT MAR AN. WILLARP J. CROXALL.

T EIQTS. @TTTD The following references are or record in the file of this patent? 1 NT T TA E? TA T T Number Name pate 2,459,059 Babso lill; Jan. 11, 1949 2,474,715 Babson June 2tl l9 4 9 

1. A PROCESS FOR PREPARING COMPOUNDS OF THE FORMULA 